脉冲溅射V2O5薄膜结构和性能研究

V2O5薄膜具有很好的离子注入/退出可逆性,是最有潜力的锂离子储存层的候选材料之一,它的电学特性与制备方法、化学计量比、结构和取向等有直接关系,仔细控制工艺参量是制备出在锂电池上应用的V2O5薄膜关键。研究中采用脉冲磁控反应溅射方法,通过精确地控制氧分压、基底温度等关键工艺参量,在石英玻璃和硅片上制备V2O5薄膜。利用X射线衍射和X射线光电子谱,分析了薄膜的成分、相结构、结晶和价态情况,用原子力显微镜表征了薄膜的微观结构,用分光光度计测量从200—2500nm波段V2O5薄膜纯度高、相结构单一、结晶度好。高低温电阻变化2个量级,薄膜的光学能隙为2.46eV。     

H2O对N复合氧化膜Cr2O3作用机制的理论研究

本文基于第一性原理方法,研究水对N复合氧化膜Cr2O3的作用机制。结果表明N的复合影响H2O在表面的吸附位点及吸附高度,N的溶入与Cr形成稳定作用,减缓H2O对表面Cr-O间的破坏作用,改善氧化膜表层结构,提高表面电化学稳定性。因此,N的复合可增强氧化膜对H2O的作用,同时改善氧化膜的结构稳定性,从而提高不锈钢的抗氧化性。     

A simple, quick and reliable method for TEM cross-section preparation of ceramic oxide films on thin metal substrates

We present a preparation method of cross-sectional thin foils for transmission electron microscopy (TEM). Samples are 0.1-1 m thick ceramic oxide films (CeO2, CeO2-YBa2Cu3O7 and CeO2-ZrO2/YO2-YBa2Cu3O7) epitaxially grown on 30-100 m highly textured nickel substrates. This method includes gluing the sample between a copper oxide dummy and a silicon dummy, followed by mechanical polishing and conventional ion milling. TEM cross-sectional samples obtained with this selection of dummies are electron-transparent up to a few tens of m parallel to the film surface. Several layer structures were analyzed by TEM and the results are shown. The preparation technique described here can be applied to any type of oxide film deposited on thin metal substrates.     

Analysis and self-lubricating treatment of porous anodic alumina film formed in a compound solution

A porous anodic film on aluminum was prepared in a mixed electrolyte of phosphoric acid and organic acid and cerium salt, and ultrasonic impregnation technology was applied on it to form self-lubricating surface composite. The structure and chemical composition of the film and its lubricity after self-lubricating treatment were investigated in detail. EPMA indicates the cross-section of anodized film has two distinct oxide layers. Al, O and P are found in the film with different distribution in the two layers. XPS analysis on the electron binding energy of the component elements show the chemical composition of film surface are Al₂O₃, Ce(OH) and some phosphates. The structure of anodized film is amorphous with XRD analysis.The tribological tests shows the frictional coefficient of the self-lubricating surface composite coating is 0.25, much lower than anodized aluminum and aluminum substrate, which is about 0.55 and 0.85, respectively, and it is also durable for a long period of time in comparison with the lubricating coating fabricated by hot-dipping method. SEM images show some PTFE particles are added into the nanoholes of anodic oxide film.     

Fe-Cr-Al合金氧化膜形成机理电子理论研究

通过自编软件建立了Fe-Cr-Al合金表面、氧化膜/基体界面模型,采用递归法计算了合金元素在Fe-Cr-Al合金表面、氧化膜/基体界面的环境敏感镶嵌能、亲和能、结合能、态密度等电子结构参数.从电子层次系统研究了Fe-Cr-Al合金氧化膜的形成机理、稀土元素和杂质硫对氧化膜形成过程及黏附性的影响机理.研究表明Fe-Cr-Al合金中Al的偏聚驱动力远大于Y,Cr.氧化初期氧从合金表面向合金内部扩散,合金内部Al向合金表面扩散,使合金形成富铝、氧表面层;氧与Al间的亲和力较大（亲和能低）,氧原子容易与Al结合生成Al₂O₃保护膜;合金中加入Y后,Y在合金表面偏聚,抑制Al向合金表面扩散,氧化膜的横向生长得到有效控制,从而避免氧化膜皱褶形貌的发生,提高氧化膜的黏附性;合金内部的S通过扩散汇集在基体/氧化膜界面,S使界面区原子的总能增高,总态密度降低,减小了界面的稳定性,进而削弱氧化膜与合金基体的结合力. 关键词： 电子结构 高温氧化 Fe-Cr-Al合金     

Electrostatic field enhancement of Al(111) oxidation

We show that the electrostatic charging of an aluminum oxide film by electron-bombardment produces a greatly enhanced rate of Al(111) oxidation by O2(g) at 90 K, compared to a film which has not been bombarded by electrons. This novel memory effect for prior electron irradiation is caused by the negative electrostatic potential created and stored on the outer oxide film surface as a result of electron bombardment. The high electrostatic field ( approximately 10(7) V/cm) produced across the depth of the film is postulated to cause an enhancement of ion migration through the film, leading to rapid oxide film growth, as predicted by the Cabrera-Mott theory of low temperature metal oxidation.     

Contact instability in adhesion and debonding of thin elastic films

Based on experiments and 3D simulations, we show that a soft elastic film during adhesion and debonding from a rigid flat surface undergoes morphological transitions to pillars, labyrinths, and cavities, all of which have the same lateral pattern length scale, lambda close to lambda/H approximately 3 for thick films, H > 1 microm . The linear stability analysis and experiments show a new thin film regime where lambda/H approximately equal to 3 + 2pi(lambda/3 muH)1/4 (gamma is surface tension, mu is shear modulus) because of a significant surface energy penalty (for example, lambda/H approximately equal to 6 for H = 200 nm; mu = 1 MPa).     

Elastic alpha-12C scattering and the 12C(alpha,gamma)16O E2 S factor

Angular distributions of 12C(alpha,alpha)12C have been measured for E(alpha) = 2.6-8.2 MeV, at angles from 24 to 166, yielding 12 864 data points. R-matrix analysis of the ratios of elastic scattering yields a reduced width amplitude of gamma12 = 0.47 +/- 0.06 MeV(1/2) for the Ex = 6.917 MeV (2+) state in 16O(a = 5.5 fm). The dependence of the chi2 surface on the interaction radius a has been investigated and a deep minimum is found at a = 5.42(+0.16)(-0.27) fm. Using this value of gamma12, radiative alpha capture and 16N beta-delayed alpha-decay data, the S factor is calculated at E(c.m.) = 300 keV to be S(E2)(300) = 53(+13)(-18) keV b for destructive interference between the subthreshold resonance tail and the ground state E2 direct capture.     

Fe-Cr-Al合金高温氧化行为电子理论研究

从电子层面系统研究Fe-Cr-Al合金氧化膜的形成机理,杂质硫对氧化膜黏附性的影响,稀土元素在改善氧化膜黏附性方面的作用,揭示合金氧化的物理本质.研究表明氧使Al在合金表层的环境敏感镶嵌能最低,促使Al原子从合金内部向合金表面扩散,最终在合金表面偏聚.由于氧与Al间的亲和力较大,氧原子易与Al结合生成Al2O3保护膜.杂质S在基体/氧化膜界面的环境敏感镶嵌能较低,可通过扩散偏聚在基体/氧化膜界面,削弱氧化膜与合金基体的结合力.当合金中加入Y后,Y易与S结合形成稳定的硫化物,阻碍S向基体/氧化膜界面的偏聚,显著提高氧化膜的黏附性,提高合金抗高温氧化能力.     

用电化学沉积法制备ZnO/Cu2O异质p-n结

由于P型ZnO的制备仍然存在一定的困难,限制了ZnO在光电方面的应用,尤其是在发光二极管和激光器的实际应用,目前利用P型的透明半导体氧化物与n型ZnO制备异质p-n结,成为新的研究热点。选择P型导电Cu2O与ZnO制备出异质p-n结。Cu2O是一种典型的P型半导体材料,禁带宽度为2．1eV,可见光范围的吸收系数较高。首次利用电化学沉积的方法制备了ZnO／Cu2O异质p-n结,研究了电沉积ZnO,Cu2O的生长机制和ZnO／Cu2O异质结的结构、光学和电学特性。     

Nb-Al合金高温氧化机理

通过自编软件建立了铝氧化膜与基体铌界面的原子集团模型,用递归法计算了合金的原子埋置能、原子结合能等电子参数,从电子层面分析铌合金高温氧化机理.研究表明:铝通过晶界扩散偏聚在合金表面,并与氧结合生成致密的Al2O3氧化膜,阻挡氧向铌基体扩散.晶界和稀土元素能提高氧化膜与基体间的原子结合能,增加其界面的结合强度,加强氧化膜与基体铌间的黏附性.因此,通过在合金中添加稀土元素或细化合金晶粒均能提高铌合金的抗高温氧化性能.     

光谱学研究硅烷钒锆复合钝化膜的结构和成膜机理

在热镀锌钢板表面制备了硅烷钒锆复合钝化膜。用X射线光电子能谱(XPS)、射频辉光放电发射光谱(rf-GD-OES)和傅里叶变换衰减全反射红外光谱(ATR-FTIR)表征了钝化膜的组成结构,分析了硅烷钒锆复合钝化膜的成膜机理。结果表明：硅烷之间互联构成了硅烷钒锆复合钝化膜的主成膜成分,无机缓蚀剂均匀分布在膜层中。钝化膜表面Si2p的XPS窄幅扫描谱100.7 eV处的拟合峰和红外光谱在波数1 100 cm-1 Si—O吸收峰变宽加强,表明硅烷以Si—O—Zn键的形式化学吸附在锌的表面,硅烷分子之间通过Si—O—Si键相互交联;红外光谱中1 650和1 560 cm-1的两个酰胺特征峰,结合910 cm-1的环氧特征峰的消失,表明γ-GPT的环氧基团在氨基活性氢的诱导下开环和γ-APT的氨基之间发生聚合反应形成交联的空间网状结构;rf-GD-OES分析发现钝化膜0.3 μm处存在一层富氧层,钝化反应生成的ZrF₄,ZrO₂和钒盐等无机物均匀分布在钝化膜中。分析膜层组成结构和成膜前后的ATR-FTIR光谱,研究了成膜过程中发生的物理过程和化学变化,提出了硅烷钒锆复合钝化膜的成膜机理。     

Experimental evidence of crystallization pressure inside porous media

Crystallization pressure of salt in porous materials is one of the mechanisms that may induce serious damage, for example, weathering of buildings and monuments of cultural heritage. Since this pressure also causes the solubility of the salt inside a porous material to differ from the bulk solubility, it can be assessed experimentally by measuring the solubility inside the pores. We show that this is possible by NMR, and study Na(2)CO(3) and Na(2)SO(4) in a series of model porous materials. Using the solubility data the crystal-liquid surface energies are estimated as gamma = 0.09 N/m for Na(2)CO(3) . 10H(2)O and gamma = 0.06 N/m for Na(2)SO(4) . 10H(2)O. For pore sizes below about 30 nm, the resulting pressure exceeds the tensile strength of typical building materials (3 MPa). No pressure is induced by the metastable Na(2)SO(4) . 7H(2)O, which suggests for this crystal a value of gamma close to zero.     

PIIID复合强化处理轴承钢表面TiN膜层的XPS表征

用等离子体浸没离子注入与沉积(PIIID)复合强化新技术在AISI52100轴承钢基体表面成功合成了硬而耐磨的氮化钛薄膜。膜层表面的化学组成和相结构分别用X射线衍射(XRD)和X射线光电子能谱(XPS)表征;膜层表面的原子力显微镜(AFM)形貌显示出TiN膜结晶完整,结构致密均匀。XRD测试结果表明,TiN在(200)晶面衍射峰最强,具有择优取向。Ti(2p)的XPS谱峰泰勒拟合分析揭示出,Ti(2p_1/2)峰和Ti_2p3/2峰均有双峰出现,表明氮化物中的Ti至少存在不同的化学状态;N(1s)的XPS谱峰在396.51, 397.22和399.01 eV附近出现了三个分峰,分别对应于TiNO_y,TiN和N—N键中的氮原子。结合O(1s)的XPS结果,证实膜层中除生成有稳定的TiN相外,还有少量钛的氧化物和未参与反应的单质氮。整个膜层是由TiN,TiO₂,Ti—O—N化合物和少量单质氮组成的复合体系。     

The interaction of H2O molecules with iron films studied with MIES,UPS and XPS

X-Ray Photoelectron Spectroscopy (XPS), Metastable Induced Electron Spectroscopy (MIES) and Ultraviolet Photoelectron Spectroscopy (UPS) were applied to study the interaction of H₂O molecules with iron films.During the interaction with H₂O molecules under ultrahigh vacuum conditions, an oxide film is formed on the iron surface. UPS and XPS still show metallic contributions, even for a surface which is exposed to about 10³ L. The oxide film thickness amounts to about 1.8 nm. No hydroxide formation is observed at all, neither in UPS nor in MIES. Further impinging H₂O molecules do not interact with the surface, because the oxide film inhibits the dissociation of impinging molecules.H₂O exposure beyond 10⁹ L does not lead to a significant increase of the oxide layer, which saturates at a thickness of 1.8 nm. In particular, no surface hydroxide is observed at this exposure. Neither XPS UPS nor MIES reveal any indication for this.     

钛的腐蚀与钝化机理电子理论研究

建立了位错塞集引发的裂纹原子集团模型,采用递归法计算了钛的电子结构参量,并研究了氧、氯、钯等元素对钛电子结构的影响.发现氧能降低费米能级附近的态密度,使钛的物理化学活性降低.氧降低钛的原子结合能,与钛原子之间有较大的亲和力,易与钛反应形成氧化膜.Cl在钛中的稳定性及与钛的亲和力均不及氧,很难取代钛表层中的氧,使得钛的氧化膜非常稳定,不会出现过钝化现象.Pd在钛中裂纹处的环境敏感镶嵌能较低,易扩散到裂纹处,且Pd元素使H在裂纹处的环境敏感镶嵌能明显升高,有效减小H向裂纹处的扩散,提高钛的应力腐蚀抵抗力. 关键词： 钛 腐蚀 钝化 电子结构     

A low-temperature and short-annealing process for metal oxide thin film transistors using deep ultraviolet light for roll-to-roll processing

Solution-processed metal oxide semiconductors have superior electron mobility and stability than solution-processed organic semiconductors. However, their fabrication requires a very-high-temperature and long-time annealing process. In this study, we utilized deep ultraviolet (DUV) light to decrease both the temperature and time of the annealing process. High external energy is required to break the organic bonds in a metal oxide film, which is generally supplied by a high-temperature annealing process carried out for a long duration.Alternatively, the required high energy can be supplied more efficiently by irradiating the metal oxide film with DUV light for a shorter duration. In this work, we used DUV light whose peaks at 172 nm instead of the generally used mercury lamp, peaking at 254 and 185 nm. Owing to this difference, thin film transistors (TFTs) could be fabricated on silicon wafers at a lower temperature and shorter duration as compared to the conditions used in previous studies. Various conditions, such as the heating temperature, duration of DUV irradiation, and N₂ flow rate, were optimized to control the heating temperature so as to achieve a mobility of 4.44 cm²/V·s and on–off ratio of 2 × 10⁷, which are much higher than those of a transistor annealed at 300 °C for 30 min (mobility, 1.31 cm²/V·s and on–off ratio, 7 × 10⁵).     

双离子束溅射中红外SiO2薄膜热稳定性研究

通过双离子束溅射方法在蓝宝石、硅衬底上制备了单层SiO2薄膜,分析了SiO2薄膜残余应力、表面形貌、微观结构以及光学性能(可见-近红外0.4~1.2 μm和中红外3~5 μm波段)在400 ℃~1 000 ℃温度范围内的演化规律.研究结果表明:在400 ℃附近,SiO2薄膜残余应力存在局部极小值;SiO2薄膜光学性能的演化与膜层表面质量、内部残余应力及微观结构变化密切相关;经1 000 ℃高温处理后,蓝宝石窗口表面SiO2薄膜红外透射性能仍能保持很好的稳定性,且膜层表面没有出现显著的气泡、开裂等损伤形貌.该研究结果可为恶劣环境下光学窗口头罩表面薄膜系统的设计提供指导.     

Measurement of the cascade transition via the first excited state of 16O in the 12C(alpha,gamma)16O reaction, and its S factor in stellar helium burning

Radiative alpha-particle capture into the first excited, J(pi)=0+ state of 16O at 6.049 MeV excitation energy has rarely been discussed as contributing to the 12C(alpha,gamma)16O reaction cross section due to experimental difficulties in observing this transition. We report here measurements of this radiative capture in 12C(alpha,gamma)16O for center-of-mass energies of E=2.22 MeV to 5.42 MeV at the DRAGON recoil separator. To determine cross sections, the acceptance of the recoil separator has been simulated in GEANT as well as measured directly. The transition strength between resonances has been identified in R-matrix fits as resulting both from E2 contributions as well as E1 radiative capture. Details of the extrapolation of the total cross section to low energies are then discussed [S6.0(300)=25(-15)(+16) keV b] showing that this transition is likely the most important cascade contribution for 12C(alpha,gamma)16O.     

Structural and electronic properties of Fe 3+ -O 2− Pairs in KMF 3 lattices (M=Mg,Zn): Is the superposition model valid?

The geometrical and electronic properties of the tetragonal FeF 5 O 4 m complex which is likely formed in KMgF 3 and KZnF 3 fluoroperovskites have been investigated by means of Density Functional calculations. The properties of this centre are dependent on the Fe-O distance ( R ox ) and also on the distances R eq and R ax between Fe 3+ and the four equatorial F m ions and the apical F m ion respectively. The calculated equilibrium distance for the isolated Fe 3+ -O 2 m pair is equal to R ox =1.63 v + while when it is introduced in KMF 3 lattices ( M =Mg, Zn) R ox ～1.82 v + . Compared to FeF 6 3 m in KMgF 3 ( R eq = R ax =1.94 v + ) the obtained equilibrium distances R ax =2.05 v + and R eq =2.02 v + mean an outwards relaxation of 6% and 4% respectively induced by the F m M O 2 m substitution. The ratio of the associated superhyperfine ( shf ) constants of equatorial ( A eq ) and axial ( A ax ) F m ligands is A eq / A ax , 2 and thus account for an experimental fingerprint of this centre. The huge difference between A s (eq) and A s (ax) cannot be explained assuming that the law relating A s to the metal-ligand distance, R , for the octahedral FeF 6 3 m unit can be transferred to the present case involving a lower symmetry . The present analysis casts doubts on the conclusions previously reached using the empirical superposition model.